TW202302544A - Chiral n-(1,3,4-oxadiazol-2-yl)phenylcarboxamides and use thereof as herbicides - Google Patents

Abstract

Chiral N-(1,3,4-oxadiazol-2-yl)phenylcarboxamides of the general formula (I) and the use thereof as herbicides are described.

In this formula (I), X, Z, R and R ^´are radicals such as alkyl, cycloalkyl and halogen.

Description

Chiral-N-(1,3,4-oxadiazol-2-yl)phenylcarboxamides and their use as herbicides

The present invention relates to the technical field of herbicides, especially herbicides for the selective control of weeds and weeds in crops of useful plants.

WO 2012/126932 A1 and WO 2018/202535 A1 describe benzamides with herbicidal activity, which differ mainly in the nature of the N-bonded heterocyclic substituent and the substituent on the benzene ring. The substances disclosed in the two documents are (1,3,4-oxadiazol-2-yl)phenylcarboxamides, which carry different alkylsulfinyl groups at the 3rd position of the benzene ring, The stereochemistry of those chiral alkylsulfinyl groups is not specified.

However, the benzamides known from the above-cited documents generally have unfavorable characteristics with regard to their biological properties, such as herbicidal action, crop plant tolerance, toxicological and ecotoxicological properties.

It was an object of the present invention to provide alternative herbicidal active ingredients. This object is achieved by the (1,3,4-oxadiazol-2-yl)phenylcarboxamide of the present invention described below, which carries a stereochemically defined Configuration of chiral alkylsulfinyl groups.

(I) 其中取代基係定義如下： R為氫或甲基， X為Cl或甲基， R´為甲基或c-Pr， Z為CF ₃或CHF ₂。 The present invention provides N-(1,3,4-oxadiazol-2-yl)phenylcarboxamide or a salt thereof with the absolute configuration specified in formula (I)

(I) The substituents are defined as follows: R is hydrogen or methyl, X is Cl or methyl, R´ is methyl or c-Pr, Z is CF ₃ or CHF ₂ .

The compounds of the present invention are the compounds of the general formula (I), according to the Cahn-Ingold-Prelog rule, they are in the S configuration, provided that the priority of R' is lower than that of the benzene ring. This is the case, for example, for compounds of general formula (I) in which R' is methyl or cyclopropyl. Further compounds of the present invention are the compounds of the general formula (I), which are in the R configuration according to the chi-Inge-Plow law, provided that the priority of R' is higher than that of the benzene ring.

Preferred are compounds I-1 to I-16: serial number R x R´ Z I-1 h Cl Me CF ₃ I-2 h Cl Me CHF ₂ I-3 h Me Me CF ₃ I-4 Me Cl c-Pr CF ₃ I-5 Me Cl Me CF ₃ I-6 Me Cl Me CHF ₂ I-7 h Me Me CHF ₂ I-8 h Me c-Pr CF ₃ I-9 h Me c-Pr CHF ₂ I-10 h Cl c-Pr CF ₃ I-11 h Cl c-Pr CHF ₂ I-12 Me Cl c-Pr CHF ₂ I-13 Me Me Me CF ₃ I-14 Me Me Me CHF ₂ I-15 Me Me c-Pr CF ₃ I-16 Me Me c-Pr CHF ₂

Particularly preferred are compounds I-1 to I-5: serial number R x R´ Z I-1 h Cl Me CF ₃ I-2 h Cl Me CHF ₂ I-3 h Me Me CF ₃ I-4 Me Cl c-Pr CF ₃ I-5 Me Cl Me CF ₃

Very specifically preferred are compounds I-4 and I-5: serial number R x R´ Z I-4 Me Cl c-Pr CF ₃ I-5 Me Cl Me CF ₃

In all formulas specified hereinafter, substituents and symbols have the same meanings as described in formula (I), unless otherwise defined.

The compounds of general formula (I) according to the present invention can be obtained, for example, by separation of chromatographic enantiomers of racemic N-(1,3,4-oxadiazol-2-yl)phenylcarboxamide (Ia). Preparation, as described in Scheme 1. Flowchart 1:

Racemic N-(1,3,4-oxadiazol-2-yl)phenylcarboxamide (Ia) is known in principle and can be described, for example, by means of WO 2012/126932 or WO 2018/202535. Method preparation.

The compounds of the formula (I) according to the invention have excellent herbicidal activity against a broad spectrum of economically important monocotyledonous and dicotyledonous annual harmful plants.

Accordingly, the present invention also provides a method for controlling unwanted vegetation or for regulating the growth of plants, preferably in plant crops, wherein one or more compounds according to the invention are applied to plants (e.g. harmful plants, such as monocotyledonous or dicotyledonous weeds or unwanted crop plants), seeds (eg grains, seeds or vegetative propagules such as tubers or shoots) or plant growth areas (eg cultivated areas). The compounds according to the invention can be applied, for example, before sowing (if appropriate also by incorporation into the soil), before emergence or after emergence. Some representative specific examples of monocotyledonous and dicotyledonous weed flora that can be controlled by the compounds of the present invention follow, although the list is not intended to be limiting to specific species.

Genus of monocotyledonous harmful plants: Aegilops, Agropyron, Agrostis, Alopecurus, Apera, Avena ), Brachiaria, Bromus, Cenchrus, Commelina, Cynodon, Cyperus, Dracula (Dactyloctenium), Digitaria, Echinochloa, Eleocharis, Eleusine, Eragrostis, Eriochloa, Festuca, Fimbristylis, Heteranthera, Imperata, Ischaemum, Leptochloa, Lolium, Monochoria, Panicum, Paspalum, Phalaris, Phleum, Poa, Rottboellia, Sagittaria, Scutellaria (Scirpus), celiac filaria (Setaria) and sorghum (Sorghum).

Dicotyledonous weed genera: Abutilon, Amaranthus, Ambrosia, Anoda, Anthemis, Aphanes, Artemisia Artemisia, Atriplex, Bellis, Bidens, Capsella, Carduus, Cassia, Centaurea , Chenopodium, Cirsium, Convolvulus, Datura, Desmodium, Emex, Erysimum, Euphorbia Euphorbia, Galeopsis, Galinsoga, Galium, Hibiscus, Ipomoea, Kochia, Wild Sesame Lamium, Lepidium, Lindernia, Matricaria, Mentha, Mercurialis, Mullugo, Forget-me-not ( Myosotis, Papaver, Pharbitis, Plantago, Polygonum, Portulaca, Ranunculus, Raphanus, Rorippa, Rotala, Rumex, Salsola, Senecio, Sesbania, Sida, Mustard Sinapis, Solanum, Sonchus, Sphenoclea, Stellaria, Taraxacum, Thlaspi, Trifolium ), Urtica, Veronica, Viola and Xanthium.

When the compounds of the present invention are applied to the soil surface before germination, the emergence of weed seedlings is completely prevented, or the weeds grow until they reach the cotyledon stage, but then stop growing.

If the active ingredient is applied to the green parts of the plant after emergence, growth ceases after the treatment and the harmful plants remain in the vegetative stage at the time of application, or they die completely after a certain time, so can be treated in this way very early and Eliminates competition from weeds harmful to crop plants in a sustainable manner.

The compounds of the invention are selective for crops of useful plants and can also be used as non-selective herbicides.

The active ingredients can also be used for controlling harmful plants in crops of genetically modified plants (which are known or have yet to be developed) due to their herbicidal and plant growth regulating properties. In general, transgenic plants are characterized by particularly advantageous properties, such as resistance to specific active ingredients used in the agrochemical industry, especially to specific herbicides, to plant diseases or pathogens of plant diseases, such as specific insect or resistance to microorganisms such as fungi, bacteria or viruses. Other specific characteristics relate to aspects such as quantity, quality, storability, composition and specific ingredients of the harvested material. For example, known transgenic plants having increased starch content or altered starch quality, or such plants having a different fatty acid composition in the harvested material. A further specific property is tolerance or resistance to abiotic stress factors such as heat, cold, drought, salinity and ultraviolet radiation.

Preference is given to using the compounds of the formula (I) according to the invention in transgenic crops of economically important useful plants and ornamental plants.

The compounds of the formula (I) can be used as herbicides in crops of useful plants which are made resistant or rendered resistant to the phytotoxic effects of herbicides by genetic engineering.

Conventional means of producing novel plants with improved properties compared to existing plants include, for example, traditional cultivation methods and the generation of mutants. Alternatively, novel plants with improved properties can be generated by means of recombinant methods (see eg EP 0221044, EP 0131624). For example, several cases of genetically modified crop plants for the purpose of modifying starch synthesis in plants have been described (eg WO 92/011376 A, WO 92/014827 A, WO 91/019806 A), via " Gene stacking" for specific herbicides glufosinate-ammonium type (see for example, EP 0242236 A, EP 0242246 A) or glyphosate type (WO 92/000377 A) or sulfonylurea type (EP 0257993 A, US 5,013,659) or Genetically modified crop plants that are resistant to combinations or mixtures of these herbicides, for example transgenic crop plants such as maize or soybean with the trade name or designation Optimum ^™ GAT™ (Glyphosate ALS Tolerance). - transgenic crop plants (eg cotton) producing Bacillus thuringiensis toxin (Bt toxin), which render the plant resistant to specific pests (EP 0142924 A, EP 0193259 A), - with modified fatty acids Composition of genetically modified crop plants (WO 91/013972 A), - Genetically modified crop plants with novel constituents or secondary metabolites (eg novel phytoalexins causing increased disease resistance) (EP 0309862 A, EP 0464461 A), - genetically modified plants with reduced photorespiration, which have higher yields and higher stress tolerance (EP 0305398 A), - genetically modified crop plants producing pharmaceutically or diagnostically important proteins ("Molecular "molecular pharming"), - transgenic crop plants characterized by higher yields or better quality, - transgenic crop plants characterized, for example, by combinations of novel properties as described above ("gene stacking") .

In principle, various molecular biology techniques are known which can be used to generate novel transgenic plants with improved properties; see for example, I. Potrykus and G. Spangenberg (eds), Gene Transfer to Plants, Springer Lab Manual (1995) ; Springer Verlag Berlin, Heidelberg or Christou, "Trends in Plant Science" 1 (1996) 423-431).

For such recombination manipulations, nucleic acid molecules allowing mutations or sequence changes by DNA sequence recombination can be introduced into plastids. By means of standard methods it is possible, for example, to carry out base exchanges, to remove partial sequences or to add natural or synthetic sequences. To join DNA fragments to each other, zygotes or linkers can be added to the fragments, see, e.g., Sambrook et al., 1989, Molecular Cloning, A Laboratory Manual, 2nd ed., Cold Spring Harbor Laboratory Press, Cold Spring Harbor, NY or Winnacker "Gene und Klone" [Genes and Clones], VCH Weinheim, 2nd ed., 1996.

For example, plant cells with reduced gene product activity can be produced by expressing at least one corresponding antisense RNA, sense RNA for co-suppression, or by expressing at least one appropriately constructed ribozyme (specific Sexual cleavage of transcripts of the above-mentioned gene products) is achieved. For this, DNA molecules covering the entire coding sequence of the gene product (including any flanking sequences that may be present) as well as DNA molecules covering only parts of the coding sequence, which in this case must be of sufficient length to be used in the Antisense effect in cells. DNA sequences that have a high degree of homology to, but not identical to, the coding sequence of a gene product may also be used.

When expressing nucleic acid molecules in plants, the synthesized protein can be localized in any desired compartment of the plant cell. However, to achieve localization in a specific compartment, for example the coding region may be joined to a DNA sequence which ensures localization in the specific compartment. Such sequences are known to those skilled in the art (see for example, Braun et al., EMBO J. 11 (1992), 3219-3227; Wolter et al., Proc. Natl. Acad. Sci. USA 85 (1988), 846- 850; Sonnewald et al., Plant J. 1 (1991), 95-106). Nucleic acid molecules can also be expressed in organelles of plant cells.

Transgenic plant cells can be regenerated by known techniques to produce whole plants. In principle, plants of any desired plant species are possible, ie not only monocots but also dicotyledons. Thus, transgenic plants can be obtained, the properties of which are altered by overexpressing, suppressing or suppressing homologous (=natural) genes or gene sequences or expressing heterologous (=foreign) genes or gene sequences.

Compound (I) of the present invention can be preferentially used in transgenic crops for growth regulators (such as 2,4-D, dicamba (dicamba)) or for inhibition of essential plant enzymes (such as acetyl lactate synthase (ALS) , EPSP synthase, glutamine synthase (GS) or hydroxyphenylpyruvate dioxygenase (HPPD)) or herbicides derived from sulfonylureas, glyphosate, glufosinate-ammonium or benzoyl Herbicides of the group of isoxazoles and similar active ingredients, or resistant to any desired combination of these active ingredients.

The compounds according to the invention can be used with particular preference in transgenic crop plants which are resistant to combinations of glyphosates and glufosinates, glyphosate and sulfonylureas or imidazolinones. Optimally, the compounds of the invention may be used in transgenic crop plants such as maize or soybean, for example under the tradename or designation Optimum ^™ GAT™ (Glyphosate ALS Tolerance).

When the active ingredients of the present invention are used in genetically modified crops, they not only affect harmful plants observed in other crops, but often also affect specific applications in specific genetically modified crops, such as controllable changes Or a particularly expanded weed spectrum, altered application rates available for application, preferably good combinability with herbicides resistant to transgenic crops and effects on growth and yield of transgenic crop plants.

The present invention therefore also relates to the use of the compounds according to the invention as herbicides for controlling harmful plants in transgenic crop plants.

The compounds according to the invention can be applied in the form of wettable powders, emulsifiable concentrates, sprayable solutions, dust products or granules in customary formulations. Accordingly, the present invention also provides herbicidal and plant growth regulating compositions comprising the compounds of the invention.

The compounds of the invention can be formulated in various ways depending on the desired biological and/or physicochemical parameters. Possible formulations include, for example: wettable powders (WP), water-soluble powders (SP), water-soluble concentrates, emulsifiable concentrates (EC), emulsions (EW) (e.g. oil-in-water and water-in-oil emulsions) , sprayable solutions, suspension concentrates (SC), oil- or water-based dispersions, oil-soluble solutions, capsule suspensions (CS), powder products (DP), dressings, granules for diffusion and soil application, in the form of Granules in the form of microparticles (GR), spray granules, absorption and adsorption granules, water dispersible granules (WG), water soluble granules (SG), ULV formulations, microcapsules and waxes. Their individual formulation types are known in principle and described, for example: Winnacker-Küchler, "Chemische Technologie" [Chemical Technology], Volume 7, C. Hanser Verlag Munich, 4th Ed. 1986; Wade van Valkenburg, "Pesticide Formulations", Marcel Dekker, N.Y., 1973; K. Martens, "Spray Drying" Handbook, 3rd Ed. 1979, G. Goodwin Ltd. London.

Required formulation aids such as inert materials, surfactants, solvents and other additives are likewise known and described in, for example: Watkins, "Handbook of Insecticide Dust Diluents and Carriers", 2nd ed., Darland Books, Caldwell N.J.; H.v. Olphen, "Introduction to Clay Colloid Chemistry", 2nd ed., J. Wiley & Sons, N.Y.; C. Marsden, "Solvents Guide", 2nd ed., Interscience, N.Y. 1963; McCutcheon's "Detergents and Emulsifiers Annual" , MC Publ. Corp., Ridgewood N.J., Sisley and Wood, "Encyclopedia of Surface Active Agents", Chem. Publ. Co. Inc., N.Y. 1964; Schönfeldt, "Grenzflächenaktive Äthyleneoxid addukte" [Interface-active Ethylene Oxide Adducts], Wiss . Verlagsgesell., Stuttgart 1976; Winnacker-Küchler, "Chemische Technologie", Volume 7, C. Hanser Verlag Munich, 4th ed. 1986.

On the basis of these formulations, combinations with other active ingredients (e.g. insecticides, acaricides, herbicides, fungicides) as well as combinations with safeners, fertilizers and/or growth regulators can also arise , for example in the form of finished formulations or tank mixes.

Wettable powders are homogeneously dispersible preparations in water which, in addition to active ingredients and diluents or inert substances, also contain ionic and/or nonionic surfactants (wetting agents, dispersing agents), such as polyethoxylated Alkylphenols, polyethoxylated fatty alcohols, polyethoxylated fatty amines, fatty alcohol polyglycol ether sulfates, alkane sulfonates, alkylbenzene sulfonates, sodium lignosulfonate, 2,2' - Sodium dinaphthylmethane-6,6'-disulfonate, sodium dibutylnaphthalenesulfonate or other sodium oleyl methyl taurate. To produce wettable powders, the active herbicidal ingredients are ground finely, for example, in customary apparatus (eg hammer mills, blower mills and air-jet mills) and mixed simultaneously or subsequently with formulation auxiliaries.

Emulsifiable concentrates are prepared by dissolving the active ingredient in an organic solvent (such as butanol, cyclohexanone, dimethylformamide, xylene, or other relatively high-boiling aromatic or hydrocarbon) or a mixture of organic solvents. Produced wherein one or more ionic and/or nonionic surfactants (emulsifiers) are added. Examples of emulsifiers which can be used are: calcium alkylarylsulfonates (e.g. calcium dodecylbenzenesulfonate), or nonionic emulsifiers, such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, Fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan esters (such as sorbitan fatty acid esters) or polyoxyethylene sorbitan esters (such as polyoxyethylene Ethylene Sorbitan Fatty Acid Ester).

Dust products are obtained by grinding the active ingredient with finely divided solids, such as talc, natural clays such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.

Suspension concentrates may be water or oil based. It can be produced, for example, by wet grinding with the aid of a commercial sand mill, optionally with the addition of surfactants, such as those listed above for other formulation types.

Emulsions such as oil-in-water emulsions (EW) can be produced, for example, by agitators, colloid mills and/or static mixers using aqueous organic solvents and optionally surfactants listed above for, for example, other formulation types.

Granules can be formulated by spraying the active ingredient onto an absorbent granular inert material or by applying the active ingredient concentrate to a carrier (e.g. sand, kaolin) with the aid of a binder (e.g. polyvinyl alcohol, sodium polyacrylate or other mineral oil). stone or granular inert material) surface. Suitable active ingredients can also be granulated in the customary way to produce fertilizer granules - if desired, as a mixture with fertilizers.

Water-dispersible granules are generally produced by customary methods such as spray drying, fluid bed granulation, pan granulation, mixing with high-speed mixers and extrusion without solid inert material.

For the production of disk granules, fluidized bed granules, extruder granules and spray granules, see, for example, the following method: "Spray-Drying Handbook" 3rd ed. 1979, G. Goodwin Ltd., London, J.E. Browning, "Agglomeration" , Chemical and Engineering 1967, pp. 147ff.; "Perry's Chemical Engineer's Handbook", 5th Ed., McGraw-Hill, New York 1973, pp. 8-57.

For additional details on the formulation of crop protection compositions see, e.g., G.C. Klingman, "Weed Control as a Science", John Wiley and Sons, Inc., New York, 1961, pp. 81-96 and J.D. Freyer, S.A. Evans , "Weed Control Handbook", 5th Ed., Blackwell Scientific Publications, Oxford, 1968, pp. 101-103.

The agrochemical formulations generally contain 0.1% to 99% by weight, especially 0.1% to 95% by weight, of the compounds according to the invention. In wettable powders, the active ingredient concentration is, for example, about 10% to 90% by weight, the remainder constituting 100% by weight consisting of customary formulation ingredients. In emulsifiable concentrates, the active ingredient concentration may be about 1% to 90% by weight, and preferably 5% to 80% by weight. Powder formulations contain 1% to 30% by weight of active ingredient, preferably usually 5% to 20% by weight of active ingredient; sprayable solutions contain about 0.05% to 80% by weight, preferably 2% by weight. % to 50% by weight of active ingredient. In the case of water-dispersible granules, the active ingredient content depends partly on whether the active compound is in liquid or solid form and on which granulation aids, fillers etc. are used. In water-dispersible granules, the content of active ingredient is, for example, between 1% and 95% by weight, preferably between 10% and 80% by weight.

Furthermore, the active ingredient formulations mentioned contain the various customary adhesives, wetting agents, dispersants, emulsifiers, penetrants, preservatives, antifreeze agents and solvents, fillers, carriers and dyes, defoamers, Evaporation inhibitors and reagents affecting pH and viscosity.

Based on their formulations, combinations with other pesticidally active substances (e.g. insecticides, acaricides, herbicides, fungicides) as well as with safeners, fertilizers and/or growth regulators are also possible, e.g. in finished formulations Or in the form of barrel mix.

For application, formulations in commercial form are diluted, if appropriate, in the customary manner, for example with water in the case of wettable powders, emulsifiable concentrates, dispersions and water-dispersible granules. Dust-form formulations, granules for soil application or granules for broadcasting and sprayable solutions are generally not diluted further with other inert substances before application.

The required rate of application of the compound of formula (I) will vary with external conditions including, inter alia, temperature, humidity and the type of herbicide used. It can vary within wide limits, for example between 0.001 and 1.0 kg/ha or more active substance, but it is preferably between 0.005 and 750 g/ha, more preferably between 0.01 and 1.5 kg/ha, more preferably 0.05 to 1 kg/ha. This applies to both pre-emergence and post-emergence applications.

Carriers are natural or synthetic, organic or inorganic substances in which the active ingredients are mixed or combined for better applicability, especially to plants or plant parts or seeds. The carrier (which may be solid or liquid) is generally inert and should be suitable for use in agriculture.

Suitable solid or liquid carriers include, for example, ammonium salts and natural rock powders, such as kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and synthetic rock powders, such as Finely crushed silica, alumina and silicates, natural or synthetic, resins, waxes, solid fertilizers, water, alcohols (especially butanol), organic solvents, mineral and vegetable oils and their derivatives. Mixtures of such carriers may likewise be used. Suitable solid carriers for granules include, for example, crushed and fractionated natural rocks, such as calcite, marble, pumice, sepiolite, dolomite, and synthetic granules of inorganic and organic powders, and granules of organic materials, such as sawdust, coconut Husks, corncobs and tobacco stems.

Suitable liquefied gaseous extenders or carriers are liquids which are gaseous at standard temperature and atmospheric pressure, such as aerosol propellants, such as halogenated hydrocarbons, or butane, propane, nitrogen and carbon dioxide.

In formulations, viscosifiers such as carboxymethylcellulose, natural and synthetic polymers in powder, granule or latex form, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, or natural phospholipids such as ceria Phospholipids and lecithins, and synthetic phospholipids. Other additives may be mineral and vegetable oils.

When the extender used is water, it is also possible to use, for example, organic solvents as auxiliary solvents. Applicable liquid solvents are mainly: aromatic hydrocarbons (such as xylene, toluene or alkylnaphthalene), chlorinated aromatic hydrocarbons or chlorinated aliphatic hydrocarbons (such as chlorobenzene, vinyl chloride or methylene chloride), aliphatic hydrocarbons (such as cyclohexane) or Paraffins (such as mineral oil fractions), mineral and vegetable oils, alcohols (such as butanol or ethylene glycol) and their ethers and esters, ketones (such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone ), strong polar solvents (such as dimethylformamide and dimethyloxide), and water.

The composition of the present invention may additionally contain other components such as surfactants. Suitable surfactants are ionic or nonionic emulsifiers and/or foam formers, dispersants or wetting agents or mixtures of these surfactants. Examples thereof are salts of polyacrylic acid, lignosulfonic acid, phenolsulfonic acid or naphthalenesulfonic acid, polycondensates of ethylene oxide with fatty alcohols, fatty acids or fatty amines, substituted phenols (preferably is alkylphenol or arylphenol), salt of sulfosuccinate, taurine derivative (preferably alkyl taurate), polyethoxylated alcohol or phosphate ester of phenol, fat of polyol Esters and derivatives of compounds containing sulfates, sulfonates and phosphates (such as alkyl aryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates, protein hydrolysates, lignosulfite waste liquor and methyl cellulose). The presence of a surfactant is necessary if one of the active ingredients and/or one of the inert carriers is insoluble in water and when the application is carried out in water. The ratio of the surfactant is between 5 and 40% by weight of the composition of the present invention. Dyes may be used, such as inorganic pigments (such as iron oxide, titanium oxide, and Prussian Blue), as well as organic dyes (such as alizarin dyes, azo dyes, and metal phthalocyanine dyes ( metal phthalocyanine dyes), and micronutrients (such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc).

If appropriate, other additional components may also be present, for example, protective colloids, binders, binders, thickeners, thixotropic substances, penetrants, stabilizers, chelating agents, complex forming agents agent. In general, the active ingredient may be combined with any solid or liquid additive commonly used for formulation purposes. Generally, the compositions and formulations of the present invention contain between 0.05% and 99% by weight, between 0.01% and 98% by weight, preferably between 0.1% and 95% by weight, More preferably between 0.5% and 90% by weight of active ingredient, optimally between 10% and 70% by weight. The active ingredients or compositions of the present invention can be used as such, or, depending on their individual physical and/or chemical properties, in the form of their formulations or use forms formulated therefrom, for example, aerosols, capsule suspensions , cold-spray concentrates, warm-spray concentrates, coated granules, fine granules, flowable concentrates for seed treatment, ready-to-use solutions, dustable powders, emulsifiable concentrates, oil-in-water Emulsions, water-in-oil emulsions, macrogranules, microgranules, oil-dispersible powders, oil-miscible flowable concentrates, oil-miscible liquids, foams, pastes, insecticide-coated seeds, suspensions Concentrates, suspoemulsion concentrates, soluble concentrates, suspensions, sprayable powders, soluble powders, powders and granules, water soluble granules or lozenges, water soluble powders for seed treatment, wettable powders, active ingredients for impregnation Natural products and synthetic substances, as well as microcapsules encapsulated in polymeric substances and coating substances for seeds, as well as ULV cold-fog and warm-fog formulations.

The formulations mentioned can be produced in known manner, for example, by mixing the active ingredients with at least one customary extender, solvent and/or diluent, emulsifier, dispersant and/or binder or fixative, wetting agent , water repellant, optional desiccant (siccative) and UV stabilizer, optional dyes and pigments, defoamers, preservatives, secondary thickeners, tackifiers, gibbex and other processing aids.

The compositions of the invention include not only ready-to-use formulations which can be applied to plants or seeds using suitable equipment, but also commercial concentrates which must be diluted with water before use.

The active ingredients of the invention can be present as such or in their (commercial standard) formulations or in their formulations with other (known) active ingredients (e.g. insecticides, attractants, infertility agents, bactericides , acaricides, nematocides, fungicides, growth regulators, herbicides, fertilizers, safeners or signal compounds) in the form of preparation.

In the present invention, the treatment of plants and plant parts with active ingredients or compositions is effected directly or on their surroundings, habitats or storage spaces by customary treatment methods, for example, by soaking, spraying, atomizing, irrigation, Evaporation, dusting, fogging, sowing, foaming, brushing, distribution, watering (soaking), drip irrigation (drip irrigating) and for propagation materials, especially seeds, can also be treated by drying seeds, Wet seed treatment, slurry treatment, incrustation, coating with one or more layers of coating, etc. Active ingredients can also be formulated by the ultra-low volume method or injected into the soil with active ingredient preparations or the active ingredient itself.

One of the advantages of the present invention is the specific bulk properties of the active ingredients and compositions of the invention, meaning that the treatment of seeds with these active ingredients and compositions not only protects the seeds themselves, but also protects the resulting plants after emergence from phytopathogenic fungi damage. Therefore, treat crops immediately at sowing or directly shortly after sowing.

It is likewise considered advantageous that the active ingredients or compositions according to the invention can also be used, inter alia, in transgenic seeds, in which case the plants grown from the seeds express proteins which are resistant to pests. Treating such seeds with the active ingredient or composition of the present invention can result in the control of specific pests only by expressing proteins (such as insecticidal proteins). Surprisingly, a further synergistic effect can be observed in this case, which additionally increases the effectiveness against infestation by pests.

The composition of the invention is suitable for protecting the seeds of any plant species used in agriculture, greenhouse, forestry or horticulture and viticulture. In particular, it is cereals (such as wheat, barley, rye, triticale, sorghum/millet and oats), corn, cotton, soybeans, rice, potatoes, sunflowers, beans, coffee, sugar beets (such as sugar beet and fodder beet), Seeds of peanuts, rapeseed, poppies, olives, coconuts, cocoa, sugar cane, tobacco, vegetables (eg tomato, cucumber, onion and lettuce), turf and ornamental plants (see also below). The treatment of cereal seeds (eg wheat, barley, rye, triticale and oats), maize and rice seeds is of particular importance.

As also described below, the treatment of genetically modified seeds with the active ingredients or compositions of the present invention is of particular importance. This is relevant to the seeds of plants containing at least one heterologous gene enabling the expression of polypeptides or proteins with insecticidal properties. The heterologous gene in the transgenic seed can be derived from, for example, microorganisms of the following genera: Bacillus, Rhizobium, Pseudomonas, Serratia, Trichoderma ( Trichoderma), Clavibacter, Glomus or Gliocladium. The heterologous gene is preferably derived from the genus Bacillus, in which case the gene product is effective against European corn borer and/or western corn rootworm. The heterologous gene is preferably derived from Bacillus thuringiensis.

In the context of the present invention, the compositions according to the invention are applied to the seed either alone or in an adapted formulation. Preferably, the seed is handled in a state in which it is sufficiently stable that no damage occurs during handling. In general, the seed can be treated at any time between harvest and sowing. It is customary to use the seeds separated from the plant without cobs, husks, stems, skins, hairs or pulp. For example, seeds that have been harvested, cleaned and dried to a moisture content of less than 15% by weight may be used. Alternatively, dried seeds (eg which have been treated with water and then dried again) may also be used.

In general, when treating seeds, it must be ensured that the amount of the compositions according to the invention and/or other additives applied to the seeds is chosen such that germination of the seeds is not affected and the plants resulting therefrom are not damaged. This has to be ensured, especially in the case of active ingredients which can exhibit phytotoxic effects at specific application rates.

The compositions of the invention can be applied directly, ie without any other components and undiluted. In general, it is preferred that the composition be applied to the seed in a suitable formulation. Suitable formulations and methods for seed treatment are known to those skilled in the art and are described, for example, in the following documents: US 4,272,417 A, US 4,245,432 A, US 4,808,430, US 5,876,739, US 2003/0176428 A1, WO 2002/080675 A1, WO 2002/028186 A2.

According to the invention, the active ingredients which can be used can be converted into customary seed dressing formulations, such as solutions, emulsions, suspensions, powders, foams, slurries or other coating compositions for seeds, and ULV formulations.

They are formulated in a known manner by mixing the active ingredients with customary additives, such as customary extenders and solvents or diluents, dyes, wetting agents, dispersants, emulsifiers, defoamers, preservatives, diluents, It is produced by mixing secondary thickener, adhesive, gibesin and water.

Suitable dyes which may be present in the seed dressing formulations according to the invention are all dyes which are customary for such purposes. Poorly water-soluble pigments or water-soluble dyes may be used. Examples include dyes known under the names Rhodamine B, C.I. Red Pigment No. 112, and C.I. Red Solvent No. 1.

Suitable wetting agents which may be present in the seed dressing formulations according to the invention are all substances which promote wetting and are customary for the formulation of agrochemically active ingredients. Alkyl naphthalenesulfonates such as diisopropyl naphthalenesulfonate or diisobutyl naphthalenesulfonate can be used with preference.

Suitable dispersants and/or emulsifiers which may be present in the seed dressing formulations according to the invention are all nonionic, anionic and cationic dispersants customary for the formulation of agrochemically active ingredients. Preference is given to using nonionic or anionic dispersants or mixtures of nonionic or anionic dispersants. Suitable nonionic dispersants include, inter alia, ethylene oxide/propylene oxide block polymers, alkylphenol polyglycol ethers and tristyrylphenol polyglycol ethers, and their phosphated or sulfated derivatives. Suitable anionic dispersants are especially lignosulfonates, polyacrylates and arylsulfonate-formaldehyde condensates.

Suitable antifoams which may be present in the seed dressing formulations according to the invention are all foam-inhibiting substances customary for the formulation of agrochemically active ingredients. Silicone defoamers and magnesium stearate are preferred.

Suitable preservatives which may be present in the seed dressing formulations according to the invention are all substances which are used for such purposes in agrochemical compositions. Examples include dichlorophene and benzyl alcohol hemiformal.

Suitable secondary thickeners which may be present in the seed dressing formulations according to the invention are all substances which are used for such purposes in agrochemical compositions. Preferred examples include cellulose derivatives, acrylic acid derivatives, xanthan gum, modified clay and finely divided silica.

Suitable adhesives which may be present in the seed dressing formulations according to the invention are all customary binding agents which can be used in seed dressing products. Preferable examples include polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and methylcellulose (tylose).

The seed dressing formulations used according to the invention can be used directly or after prior dilution with water to treat a wide variety of seeds, including seeds of transgenic plants. In this case, additional synergistic effects can also be produced when interacting with the substances formed by the manifestation.

When treating seeds with the suitable seed dressing formulations according to the invention or with the preparations prepared therefrom by adding water, suitable apparatus are all mixing units customary for seed coatings. Specifically, the seed dressing procedure is to place the seeds in a mixer, add the specified desired amount of the seed dressing formulation (as it is or after prior dilution with water) and mix until the formulation is evenly distributed over the seeds . If appropriate, a drying operation follows.

The active ingredient of the present invention, when compatible with plants, has favorable homeotherm toxicity and good environmental compatibility, is suitable for protecting plants and plant organs, increasing harvest yield, and improving the quality of harvested crops. These are preferably used as crop protection agents. They are active against generally sensitive and resistant species and against all or specific stages of development.

The following examples illustrate the invention. A. Chemical Examples Description of Palmate Separation

The compounds of the invention have been prepared by chiral supercritical liquid chromatography (SFC) separation of the corresponding racemate (Ia). Separation of enantiomers was performed with a Sepiatec SFC 100 instrument. As an example, separation conditions to produce the S enantiomers 1-1, 1-2, 1-3, 1-4, 1-5 and 1-6 are described below.

The enantiomer purity of the isolated enantiomers was determined by analytical SFC system (Aquity ^UPC2 from Waters). The enantiomer excess ee is reported in the examples below. Optical rotation values were determined on a polarimeter (from Krüss).

The S configurations of compounds I-1 and I-5 were determined by single crystal x-ray structure analysis. 2-Chloro-N-(1,3,4-oxadiazol-2-yl)-3-[(S)-methylsulfinyl]-4-(trifluoromethyl)benzamide I The racemate used in the preparation of -1 : 2-chloro-N-(1,3,4-oxadiazol-2-yl)-3-[(rac)-methylsulfinyl]-4 -(Trifluoromethyl)benzamide (Ia-1) Chiral column: Chiracel OX-H for SFC; 250 x 20 mm; 5 µm (Chiracel Technologies Europe) Injection volume: 0.5 ml/injection containing 850 mg racemate 1a-1 in 19 ml acetonitrile Flow rate: 80 ml/min Solvent: CO ₂ /MeOH = 85/15 Sharp peak: 4.30 – 4.80 min (S enantiomer I-1) Analysis : S enantiomer I-1; SFC column: Chiracel OX-3 for SFC from Chiral Technologies Europe (0.3 cm x 10 cm; 3 µm) Flow rate = 2 ml/min.; _CO2 /MeOH = 90 / 10 Retention time: 1.95 min. 94% ee Optical rotation: - 64 ° (MeOH) Absolute configuration determined by single crystal x-ray structure analysis. See Figure 1. 2-Chloro-N-(1,3,4-oxadiazol-2-yl)-3-[(S)-methylsulfinyl]-4-(difluoromethyl)benzamide I The racemate used in the preparation of -2 : 2-chloro-N-(1,3,4-oxadiazol-2-yl)-3-[(rac)-methylsulfinyl]-4 -(Difluoromethyl)benzamide (Ia-2) Chiral column: Lux ^R 5 µm Amylose-1; 250 x 21.2 mm (Phenomenex) Injection volume: 0.5 ml/injection contains 675 mg racemate Solution flow rate of 1a-2 in 17 ml acetonitrile: 80 ml/min Solvent: CO ₂ /MeOH = 75/25 Sharp peak: 1.80 – 2.80 min (S enantiomer I-2) Analysis: S enantiomer I-2 SFC column: Lux Amylose 1 from Phenomenex. (0.3 cm x 150 mm; 3 µm) Flow rate = 2 ml/min.; CO ₂ /MeOH = 90 / 10 Retention time: 1.91 min >99% ee Optical rotation: -194° (CHCl ₃ ) The absolute configuration was assigned in a similar manner to 1-1 and 1-5. 2-Methyl-N-(1,3,4-oxadiazol-2-yl)-3-[(S)-methylsulfinyl]-4-(trifluoromethyl)benzamide The racemate used in the preparation of I-3 : 2-methyl-N-(1,3,4-oxadiazol-2-yl)-3-[(rac)-methylsulfinyl] -4-(Trifluoromethyl)benzamide Ia-3 Chiral column: Chiracel OX-H for SFC; 250 x 20 mm; 5 µm (Chiracel Technologies Europe) Injection volume: 0.3 ml/injection containing 1.73 mg racemate 1a-3 in 35 ml acetonitrile Flow rate: 80 ml/min Solvent: CO ₂ /MeOH = 85/15 Sharp peak: 4.70 – 5.25 min (S enantiomer I-3) Analysis : S Spiegelmer I-3 SFC Column: Chiracel OX-3 for SFC from Chiral Technologies Europe. (0.3 cm x 10 cm; 3 µm) Flow rate = 2 ml/min. (CO ₂ /MeOH = 90/10) Retention time: 1.73 min >99% ee Optical rotation: -86° (MeOH) The absolute configuration was assigned in a similar manner to I-1 and I-5. 2-Chloro-N-(5-methyl-1,3,4-oxadiazol-2-yl)-3-[(S)-cyclopropylsulfinyl]-4-(trifluoromethyl ) Racemate used in the preparation of benzamide I-4 : 2-chloro-N-(5-methyl-1,3,4-oxadiazol-2-yl)-3-[(rac )-cyclopropylsulfinyl]-4-(trifluoromethyl)benzamide 1a-4 Chiral column: Chiralpak AZH for SFC; 250 x 20 mm; 5 µm (Chiracel Technologies Europe) Injection volume : 0.5 ml/injection of a solution containing 139 mg of racemate 1a-4 in 5 ml of acetonitrile Flow rate: 80 ml/min Eluent: _CO2 /MeOH = 85/15 Peak: 10.00 – 13.50 min (S enantiomer Substance I-4) Analysis: S Spiegelmer I-4 SFC Column: Chiracel AZ-3 for SFC from Chiral Technologies Europe. (0.3 cm x 10 cm; 3 µm) Flow rate = 2 ml/min . (CO ₂ /MeOH = 90 / 10) Retention time: 2.22 min. >99% ee Optical rotation: -43 ° (CHCl ₃ ) The absolute configuration was assigned in a similar manner to I-1 and I-5. 2-Chloro-N-(5-methyl-1,3,4-oxadiazol-2-yl)-3-[(S)-methylsulfinyl]-4-(trifluoromethyl) The racemate used in the preparation of benzamide I-5 : 2-chloro-N-(5-methyl-1,3,4-oxadiazol-2-yl)-3-[(rac) -Methylsulfinyl]-4-(trifluoromethyl)benzamide 1a-5 Handy column: Lux ^R 5 µm Amylose-1; 250 x 21.2 mm (Phenomenex) Injection volume: 0.6 ml / Injection of a solution containing 100 mg of racemate 1a-5 in 2 ml of methanol Flow rate: 80 ml/min Solvent: _CO2 /MeOH = 90/10 Peak: 4.60 – 6.37 min (S enantiomer I-5 ) Analysis: S Spiegelmer I-5 SFC Column: Chiracel OX-3 for SFC from Chiral Technologies Europe (0.3 cm x 10 cm; 3 µm) Flow = 2 ml/min. (CO2/MeOH = 90 / 10) Retention time: 1.79 min >99% ee Optical rotation: -69 ° (MeOH) Absolute configuration was determined by single crystal x-ray structure analysis. See Figure 2. 2-Chloro-N-(5-methyl-1,3,4-oxadiazol-2-yl)-3-[(S)-methylsulfinyl]-4-(difluoromethyl) The racemate used in the preparation of benzamide I-6 : 2-chloro-N-(5-methyl-1,3,4-oxadiazol-2-yl)-3-[(rac) -Methylsulfinyl]-4-(difluoromethyl)benzamide 1a-6 Chiral column: Chiracel OX-H for SFC; 250 x 20 mm; 5 µm (Chiracel Technologies Europe) Injection volume: 0.5 ml/injection containing 730 mg racemate 1a-6 in 18 ml acetonitrile Flow rate: 80 ml/min Eluent: _CO2 /MeOH = 80/20 Spike: 3.45 – 4.00 min; S mirror image Isomer Analysis: S Spiegelmer I-6 SFC Column: Chiracel OX-3 for SFC from Chiral Technologies Europe (0.3 cm x 10 cm; 3 µm) Flow = 2 ml/min. CO2/ MeOH = 90 / 10 Retention time: 1.83 min. >99 % ee Optical rotation: -178 ° (CHCl ₃ ) The absolute configuration was assigned in a similar manner to I-1 and I-5.

編號 R X R´ Z 旋光度 I-1 H Cl Me CF ₃ (-)-65 ° (MeOH) I-2 H Cl Me CHF ₂ (-)-194 ° (CHCl ₃) I-3 H Me Me CF ₃ (-)-86 ° (MeOH) I-4 Me Cl c-Pr CF ₃ (-)-43 ° (CHCl ₃) I-5 Me Cl Me CF ₃ (-)-69 ° (MeOH) I-6 Me Cl Me CHF ₂ (-)-178 ° (CHCl ₃) B. 調配物實例 a)     藉由混合10重量份之式(I)化合物及/或其鹽和90重量份作為惰性物質之滑石並在錘磨機中粉碎混合物而獲得粉劑產物。 b)     藉由混合25重量份之式(I)化合物及/或其鹽、64重量份作為惰性物質之含高嶺土石英、10重量份之木質磺酸鉀和1重量份作為潤濕劑與分散劑之油醯基甲基牛磺酸鈉並在銷盤磨機中研磨混合物而獲得易於分散於水中之可濕性粉末。 c)     藉由混合20重量份之式(I)化合物及/或其鹽與6重量份之烷基酚聚二醇醚( ^®Triton X 207)、3重量份之異十三醇聚二醇醚(8 EO)和71重量份之石蠟礦物油(沸點範圍為例如約255℃至高於277℃)並在摩擦球磨機中將混合物研磨至低於5微米之細度而獲得易於水可分散之分散濃縮物。 d)     自15重量份之式(I)化合物及/或其鹽、75重量份作為溶劑之環己酮和10重量份作為乳化劑之氧乙基化壬基酚獲得可乳化濃縮物。 e)     藉由混合下列而獲得水可分散顆粒： 75重量份之式(I)化合物及/或其鹽， 10重量份之木質磺酸鈣， 5重量份之月桂基硫酸鈉， 3重量份之聚乙烯醇和 7重量份之高嶺土， 在銷盤磨機中研磨混合物，並藉由噴霧施用水作為製粒液體在流化床中使粉末製粒。 f)    亦藉由在膠體磨機中均質化與預粉碎下列而獲得水可分散顆粒： 25重量份之式(I)化合物及/或其鹽， 5重量份之2,2'-二萘基甲烷-6,6'-二磺酸鈉， 2重量份之油醯基甲基牛磺酸鈉， 1重量份之聚乙烯醇， 17重量份之碳酸鈣和 50重量份之水， 隨後在砂磨機中研磨混合物並藉由單相噴嘴將噴霧塔中所得懸浮液霧化及乾燥。 C. 生物學實例 Abbreviations used mean: Me = methyl c-Pr = Cyclopropyl Table 1 : Compounds of general formula (I) according to the invention, wherein R, X, Z and R' have the definitions given in Table 1.

serial number R x R´ Z Optical rotation I-1 h Cl Me CF ₃ (-)-65° (MeOH) I-2 h Cl Me CHF ₂ (-)-194 ° (CHCl ₃ ) I-3 h Me Me CF ₃ (-)-86° (MeOH) I-4 Me Cl c-Pr CF ₃ (-)-43 ° (CHCl ₃ ) I-5 Me Cl Me CF ₃ (-)-69° (MeOH) I-6 Me Cl Me CHF ₂ (-)-178 ° (CHCl ₃ ) B. Formulation Examples a) A powder product is obtained by mixing 10 parts by weight of a compound of formula (I) and/or its salt and 90 parts by weight of talc as an inert substance and pulverizing the mixture in a hammer mill. b) by mixing 25 parts by weight of the compound of formula (I) and/or its salt, 64 parts by weight of kaolin-containing quartz as an inert substance, 10 parts by weight of potassium lignosulfonate and 1 part by weight as a wetting agent and a dispersant Sodium oleyl methyl taurate was obtained and the mixture was ground in a pin-on-disc mill to obtain a wettable powder that was easily dispersed in water. c) by mixing 20 parts by weight of the compound of formula (I) and/or its salt with 6 parts by weight of alkylphenol polyglycol ether ( ^® Triton X 207), 3 parts by weight of isotridecanyl polyglycol ether (8 EO) and 71 parts by weight of paraffinic mineral oil (boiling point range is, for example, about 255°C to above 277°C) and the mixture is ground in a friction ball mill to a fineness below 5 microns to obtain a readily water-dispersible dispersion concentrate things. d) An emulsifiable concentrate is obtained from 15 parts by weight of a compound of formula (I) and/or its salt, 75 parts by weight of cyclohexanone as solvent and 10 parts by weight of oxyethylated nonylphenol as emulsifier. e) Water dispersible granules are obtained by mixing the following: 75 parts by weight of the compound of formula (I) and/or its salt, 10 parts by weight of calcium lignosulfonate, 5 parts by weight of sodium lauryl sulfate, 3 parts by weight of Polyvinyl alcohol and 7 parts by weight of kaolin, the mixture was ground in a pin-on-disk mill, and the powder was granulated in a fluidized bed by spraying water as granulation liquid. f) Water-dispersible granules are also obtained by homogenizing and pre-crushing in a colloid mill the following: 25 parts by weight of the compound of formula (I) and/or its salts, 5 parts by weight of 2,2'-dinaphthyl methane-6,6'-sodium disulfonate, 2 parts by weight of sodium oleyl methyl taurate, 1 part by weight of polyvinyl alcohol, 17 parts by weight of calcium carbonate and 50 parts by weight of water, then in sand The mixture is ground in a mill and the resulting suspension is atomized and dried in a spray tower by means of single-phase nozzles. C. Biological examples

The plant pest abbreviations used mean: ABUTH Abutilon theophrasti ALOMY Alopecurus myosuroides AVEFA Wild Oats (Avena fatua) AMARE Amaranth (Amaranthus retroflexus) CYPES Yellow Sedge (Cyperus esculentus) DIGSA Crabgrass (Digitaria sanguinalis) ECHCG Barnyardgrass (Echinochloa crus-galli) HORMU Sage grass (Hordeum murinum) LOLMU Ryegrass (Lolium multiflorum) LOLRI Stiff ryegrass (Lolium rigidum) MATIN Matricaria inodora PHBPU Purple Flower Morning Glory (Pharbitis purpurea) POLCO Polygonum convolvulus SETVI Setaria viridis STEME Chickweed (Stellaria media) VERPE Arabian mother-in-law (Veronica persica) VIOTR Pansy (Viola tricolor) BRSNW Rapeseed (Brassica napus (Winter Rapeseed)) GLXMA Soybean (Glycine max (Soybean)) ORYZA Rice (Oryza sativa (rice)) TRZAS Wheat (Triticum aestiva (bread wheat)) ZEAMX Corn (Zea mays (Maize)) 1. Pre-emergence herbicide against harmful plants

Seeds of monocot and dicot weed plants and crop plants were placed in sandy loam in wood fiber pots and covered with soil. Formulate the compounds according to the invention in the form of wettable powders (WP) or emulsion concentrates (EC) and subsequently apply them as aqueous suspensions or emulsions at a water application rate corresponding to 600 to 800 l/ha on the surface of the covered soil , which added 0.2% wetting agent. After treatment, the pots were placed in a greenhouse and the test plants were kept under good growing conditions. After a test period of 3 weeks, damage to the test plants was scored visually by comparison with an untreated control group (percentage (%) of herbicidal activity: 100% activity = plant dead, 0% activity = same as control similar to plants). Many of the compounds of the present invention show very good effects on many important harmful plants. The following tables illustrate by way of example the post-emergence herbicidal action of the compounds according to the invention, the herbicidal activity being expressed as a percentage. Table 1a: Pre-emergence effect of ALOMY at 20 g/ha in % instance number Dose [g/ha] ALOMY I-4 20 80 Table 1b: Pre-emergence effect of 80 g/ha on ALOMY in % instance number Dose [g/ha] ALOMY I-5 80 80 I-1 80 80 I-4 80 100 I-6 80 100 I-2 80 90 Table 2a: Pre-emergence effect of 20 g/ha on AMARE in % instance number Dose [g/ha] AMARE I-5 20 90 I-1 20 100 I-3 20 100 I-4 20 100 I-6 20 90 I-2 20 100 Table 2b: Pre-emergence effect of 80 g/ha on AMARE in % instance number Dose [g/ha] AMARE I-5 80 100 I-1 80 100 I-3 80 100 I-4 80 100 I-6 80 100 I-2 80 100 Table 3: Pre-emergence effect of AVEFA at 80 g/ha in % instance number Dose [g/ha] AVEFA I-5 80 80 I-1 80 80 I-4 80 90 I-6 80 100 I-2 80 100 Table 4a: Pre-emergence effect of DIGSA at 20 g/ha in % instance number Dose [g/ha] DIGSA I-3 20 100 I-4 20 100 I-6 20 100 Table 4b: Pre-emergence effect of 80 g/ha on DIGSA in % instance number Dose [g/ha] DIGSA I-3 80 100 I-4 80 100 I-6 80 100 Table 5a: Pre-emergence effect of ECHCG at 5 g/ha in % instance number Dose [g/ha] ECHCG I-1 5 90 Table 5b: Pre-emergence effect of ECHCG at 20 g/ha in % instance number Dose [g/ha] ECHCG I-5 20 100 I-1 20 100 I-3 20 90 I-6 20 90 I-2 20 100 Table 5c: Pre-emergence effect of 80 g/ha on ECHCG in % instance number Dose [g/ha] ECHCG I-5 80 100 I-1 80 100 I-3 80 100 I-4 80 100 I-6 80 100 I-2 80 100 Table 6: Pre-emergence effect of LOLRI at 80 g/ha in % instance number Dose [g/ha] LOLRI I-4 80 80 I-2 80 90 Table 7a: Pre-emergence effect of MATIN at 20 g/ha in % instance number Dose [g/ha] MATIN I-5 20 80 I-1 20 100 I-4 20 80 I-6 20 90 I-2 20 100 Table 7b: Pre-emergence effect of 80 g/ha on MATIN in % instance number Dose [g/ha] MATIN I-5 80 100 I-1 80 100 I-3 80 90 I-4 80 100 I-6 80 90 I-2 80 100 Table 8: Pre-emergence effect of 80 g/ha on PHBPU in % instance number Dose [g/ha] PHBPU I-5 80 100 I-1 80 100 Table 9: Pre-emergence effect of POLCO at 80 g/ha in % instance number Dose [g/ha] POLCO I-1 80 80 I-4 80 80 I-2 80 90 Table 10a: Pre-emergence effect of SETVI at 5 g/ha in % instance number Dose [g/ha] SETVI I-5 5 80 Table 10b: Pre-emergence effect of SETVI at 20 g/ha in % instance number Dose [g/ha] SETVI I-5 20 100 I-1 20 80 I-4 20 100 I-6 20 90 I-2 20 100 Table 10c: Pre-emergence effect of 80 g/ha on SETVI in % instance number Dose [g/ha] SETVI I-5 80 100 I-1 80 100 I-3 80 90 I-4 80 100 I-6 80 100 I-2 80 100 Table 11a: Pre-emergence effect of 20 g/ha on STEME in % instance number Dose [g/ha] STEME I-3 20 80 Table 11b: Pre-emergence effect of 80 g/ha on STEME in % instance number Dose [g/ha] STEME I-3 80 100 Table 12a: Pre-emergence effect of VERPE at 20 g/ha in % instance number Dose [g/ha] VERPE I-5 20 80 I-6 20 90 I-2 20 80 Table 12b: Pre-emergence effect of VERPE at 80 g/ha in % instance number Dose [g/ha] VERPE I-5 80 100 I-4 80 100 I-6 80 100 I-2 80 80 Table 13a: Pre-emergence effect of 20 g/ha on VIOTR in % instance number Dose [g/ha] VIOTR I-1 20 100 I-3 20 90 I-4 20 100 I-6 20 100 I-2 20 100 Table 13b: Pre-emergence effect of 80 g/ha on VIOTR in % instance number Dose [g/ha] VIOTR I-5 80 100 I-1 80 100 I-3 80 100 I-4 80 100 I-6 80 100 I-2 80 100 2. Post-emergence herbicide against harmful plants

Seeds of monocotyledonous and dicotyledonous weed plants and crop plants are placed in sandy loam in wood fiber pots, covered with soil, and grown in a greenhouse under favorable growing conditions. The test plants were treated at the one-leaf stage 2 to 3 weeks after sowing. Formulate the compounds according to the invention in the form of wettable powders (WP) or emulsion concentrates (EC) and subsequently spray them on the green parts of plants in the form of aqueous suspensions or emulsions at a water application rate corresponding to 600 to 800 l/ha , which added 0.2% wetting agent. After the test plants had been placed under ideal growth conditions in the greenhouse for about 3 weeks, the action of the formulation was assessed visually by comparison with the untreated control (herbicidal action percentage (%): 100% active = plant dead, 0% activity = similar to control plants). Many of the compounds of the present invention show very good effects on many important harmful plants. The following tables illustrate by way of example the post-emergence herbicidal action of the compounds according to the invention, the herbicidal activity being expressed as a percentage. Table 14a: Post-emergence effect of 1.25 g/ha on AMARE in % instance number Dose [g/ha] AMARE I-1 1.25 100 Table 14b: Post-emergence effect of 5 g/ha on AMARE in % instance number Dose [g/ha] AMARE I-5 5 100 I-1 5 100 I-3 5 90 I-4 5 100 I-6 5 90 I-2 5 100 Table 14c: Post-emergence effect of 20 g/ha on AMARE in % instance number Dose [g/ha] AMARE I-5 20 100 I-1 20 100 I-3 20 90 I-4 20 100 I-6 20 100 I-2 20 100 Table 15: Postemergence effect of AVEFA at 20 g/ha in % instance number Dose [g/ha] AVEFA I-1 20 80 Table 16a: Postemergence effect of DIGSA at 5 g/ha in % instance number Dose [g/ha] DIGSA I-3 5 90 I-4 5 90 I-6 5 90 Table 16b: Post-emergence effect of DIGSA at 20 g/ha in % instance number Dose [g/ha] DIGSA I-3 20 90 I-4 20 100 I-6 20 90 Table 17a: Postemergence effect of ECHCG at 5 g/ha in % instance number Dose [g/ha] ECHCG I-5 5 90 I-1 5 100 I-3 5 80 I-2 5 90 Table 17b: Postemergence effect of ECHCG at 20 g/ha in % instance number Dose [g/ha] ECHCG I-5 20 100 I-1 20 100 I-3 20 90 I-4 20 90 I-6 20 100 I-2 20 90 Table 18a: Postemergence effect of MATIN at 5 g/ha in % instance number Dose [g/ha] MATIN I-5 5 80 I-1 5 80 I-2 5 90 Table 18b: Postemergence effect of MATIN at 20 g/ha in % instance number Dose [g/ha] MATIN I-5 20 90 I-1 20 90 I-3 20 80 I-4 20 80 I-2 20 90 Table 19a: Post-emergence effect of 5 g/ha on PHBPU in % instance number Dose [g/ha] PHBPU I-1 5 100 I-3 5 80 Table 19b: Post-emergence effect of 20 g/ha on PHBPU in % instance number Dose [g/ha] PHBPU I-5 20 90 I-1 20 100 I-3 20 80 I-6 20 90 I-2 20 90 Table 20: Post-emergence effect of POLCO at 20 g/ha in % instance number Dose [g/ha] POLCO I-1 20 80 I-2 20 80 Table 21a: Postemergence effect of SETVI at 5 g/ha in % instance number Dose [g/ha] SETVI I-5 5 80 I-1 5 80 I-4 5 100 I-6 5 100 I-2 5 90 Table 21b: Postemergence effect of SETVI at 20 g/ha in % instance number Dose [g/ha] SETVI I-5 20 100 I-1 20 100 I-3 20 90 I-4 20 100 I-6 20 100 I-2 20 90 Table 22: Post-emergence effect of 20 g/ha on STEME in % instance number Dose [g/ha] STEME I-3 20 80 Table 23a: Post-emergence effect of VERPE at 5 g/ha in % instance number Dose [g/ha] VERPE I-6 5 90 I-2 5 90 Table 23b: Post-emergence effect of VERPE at 20 g/ha in % instance number Dose [g/ha] VERPE I-5 20 90 I-1 20 90 I-6 20 90 I-2 20 100 Table 24a: Postemergence effect on VIOTR at 1.25 g/ha in % instance number Dose [g/ha] VIOTR I-1 1.25 90 Table 24b: Post-emergence effect on VIOTR at 5 g/ha in % instance number Dose [g/ha] VIOTR I-5 5 100 I-1 5 100 I-6 5 80 I-2 5 90 Table 24c: Postemergence effect on VIOTR at 20 g/ha in % instance number Dose [g/ha] VIOTR I-5 20 100 I-1 20 100 I-3 20 90 I-6 20 100 I-2 20 100 comparative experiment

In the following experiments, the herbicidal effects of the compounds of the present invention and the corresponding known racemic compounds closest to WO2012126932 and WO2018202535 were compared under the above-mentioned specific conditions by pre-emergence and post-emergence methods. The example numbers given in each table refer to the compound disclosed in the relevant individual literature. Table 25: Pre-emergence herbicide/damage to crop plants Instance number: Dose (g ai / ha) damage ZEAMX I-1, the present invention 320 0 1-360 from WO2012126932 320 20 Instance number: Dose (g ai / ha) damage ORYZA TRZAS I-1, the present invention 80 80 30 1-360 from WO2012126932 80 100 80 Instance number: Dose (g ai / ha) damage TRZAS I-2, the present invention 20 20 Racemate, known from WO2018202535 20 70 Instance number: Dose (g ai / ha) damage GLXMA TRZAS I-2, the present invention 80 30 70 Racemate, known from WO2018202535 80 80 100 Instance number: Dose (g ai / ha) damage GLXMA ZEAMX TRZAS I-3, the present invention 80 50 0 30 1-144, obtained from WO2012126932 80 80 30 90 Instance number: Dose (g ai / ha) damage BRSNW ZEAMX TRZAS I-3, the present invention 20 70 0 0 1-144, obtained from WO2012126932 20 100 20 50 Instance number: Dose (g ai / ha) damage GLXMA ZEAMX I-4, the present invention 80 80 50 Racemate, known from WO2012126932 80 100 70 Instance number: Dose (g ai / ha) damage GLXMA I-4, the present invention 20 40 Racemate, known from WO2012126932 20 60 Instance number: Dose (g ai / ha) Herbicidal effect ALOMY AVEFA LOLRI I-4, the present invention 20 80 30 50 Racemate, known from WO2012126932 20 0 0 0 Instance number: Dose (g ai / ha) Herbicidal effect ZEAMX I-5, the present invention 320 40 2-360 from WO2012126932 320 60 Instance number: Dose (g ai / ha) Herbicidal effect STEME POLCO I-5, the present invention 320 100 80 2-360 from WO2012126932 320 70 20 Instance number: Dose (g ai / ha) Herbicidal effect STEME VERPE I-5, the present invention 80 100 100 2-360 from WO2012126932 80 70 10 Instance number: Dose (g ai / ha) Herbicidal effect ALOMY AVEFA CYPES MATIN I-5, the present invention 20 60 90 90 90 2-360 from WO2012126932 20 30 0 70 70 Instance number: Dose (g ai / ha) Herbicidal effect SETVI STEME VERPE I-5, the present invention 20 100 100 30 2-360 from WO2012126932 20 50 0 0 Instance number: Dose (g ai / ha) damage ZEAMX I-6, the present invention 80 20 7-48, obtained from WO2018202535 80 50 Instance number: Dose (g ai / ha) damage BRSNW I-6, the present invention 20 40 7-48, obtained from WO2018202535 20 80 Table 26: Post-emergence herbicidal effect/damage to cultivated plants Instance number: Dose (g ai / ha) damage ORYZA ZEAMX TRZAS I-1, the present invention 80 70 0 60 1-360 from WO2012126932 80 100 20 100 Instance number: Dose (g ai / ha) damage ZEAMX I-1, the present invention 80 0 1-360 from WO2012126932 80 20 Instance number: Dose (g ai / ha) damage ORYZA I-2, the present invention 5 0 Racemate, known from WO2018202535 5 60 I-2, Postemergence effects Instance number: Dose (g ai / ha) Herbicidal effect ECHCG I-2, the present invention 5 90 Racemate, known from WO2018202535 5 70 Instance number: Dose (g ai / ha) damage ORYZA TRZAS I-3, the present invention 5 30 20 1-144, obtained from WO2012126932 5 60 40 Instance number: Dose (g ai / ha) damage TRZAS I-3, the present invention 20 30 1-144, obtained from WO2012126932 20 50 Instance number: Dose (g ai / ha) damage BRSNW ZEAMX TRZAS I-4, the present invention 20 80 0 20 Racemate, known from WO2012126932 20 100 20 40 Instance number: Dose (g ai / ha) Herbicidal effect LOLRI DIGSA I-4, the present invention 20 60 100 Racemate, known from WO2012126932 20 30 80 Instance number: Dose (g ai / ha) Herbicidal effect VERPE I-4, the present invention 5 60 Racemate, known from WO2012126932 5 40 Instance number: Dose (g ai / ha) damage ZEAMX I-5, the present invention 20 0 2-360 from WO2012126932 20 20 Instance number: Dose (g ai / ha) Herbicidal effect SETVI STEME VERPE I-5, the present invention 5 100 80 40 2-360 from WO2012126932 5 80 0 20 Instance number: Dose (g ai / ha) Herbicidal effect CYPES I-5, the present invention 20 80 2-360 from WO2012126932 20 50 I-6 PO selectivity Instance number: Dose (g ai / ha) damage GLXMA TRZAS I-6, the present invention 5 40 20 7-48, obtained from WO2018202535 5 60 40 Instance number: Dose (g ai / ha) Herbicidal effect ECHCG VIOTR I-6, the present invention 20 100 100 7-48, obtained from WO2018202535 20 80 80 Instance number: Dose (g ai / ha) Herbicidal effect SETVI VIOTR I-6, the present invention 5 100 80 7-48, obtained from WO2018202535 5 80 60

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Figure 1 shows the single crystal x-ray structure analysis of compound I-1 of the present invention, which is 2-chloro-N-(1,3,4-oxadiazol-2-yl)-3-[(S)-methylidene Sulfonyl]-4-(trifluoromethyl)benzamide.

Figure 2 shows the single crystal x-ray structure analysis of compound 1-5 of the present invention, which is 2-chloro-N-(5-methyl-1,3,4-oxadiazol-2-yl)-3-[(S )-methylsulfinyl]-4-trifluoromethyl)benzamide.

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Claims (12)

An N-(1,3,4-oxadiazol-2-yl)phenylcarboxamide or a salt thereof in the absolute configuration specified in formula (I),

(I) The substituents are defined as follows: R is hydrogen or methyl, X is Cl or methyl, R´ is methyl or c-Pr, Z is CF ₃ or CHF ₂ . N-(1,3,4-oxadiazol-2-yl)phenylcarboxamides I-1 to I-16 of Claim 1: serial number R x R´ Z I-1 h Cl Me CF ₃ I-2 h Cl Me CHF ₂ I-3 h Me Me CF ₃ I-4 Me Cl c-Pr CF ₃ I-5 Me Cl Me CF ₃ I-6 Me Cl Me CHF ₂ I-7 h Me Me CHF ₂ I-8 h Me c-Pr CF ₃ I-9 h Me c-Pr CHF ₂ I-10 h Cl c-Pr CF ₃ I-11 h Cl c-Pr CHF ₂ I-12 Me Cl c-Pr CHF ₂ I-13 Me Me Me CF ₃ I-14 Me Me Me CHF ₂ I-15 Me Me c-Pr CF ₃ I-16 Me Me c-Pr CHF ₂ N-(1,3,4-oxadiazol-2-yl)phenylcarboxamides I-1 to I-5 of claim 1: serial number R x R´ Z I-1 h Cl Me CF ₃ I-2 h Cl Me CHF ₂ I-3 h Me Me CF ₃ I-4 Me Cl c-Pr CF ₃ I-5 Me Cl Me CF ₃ N-(1,3,4-oxadiazol-2-yl)phenylcarboxamide I-4 or I-5 of claim 1: serial number R x R´ Z I-4 Me Cl c-Pr CF ₃ I-5 Me Cl Me CF ₃ N-(1,3,4-oxadiazol-2-yl)phenylcarboxamide as claimed in claim 1, wherein the enantiomer excess (ee) is at least 94%. N-(1,3,4-oxadiazol-2-yl)phenylcarboxamide as claimed in claim 1, wherein the enantiomer excess (ee) is at least 99%. A herbicidal composition comprising at least one compound according to claim 1 mixed with a formulation adjuvant. The herbicidal composition according to claim 1, which comprises at least one other insecticidal active substance selected from the following groups: insecticides, acaricides, herbicides, fungicides, safeners and growth regulators agent. A method for controlling unwanted plants, characterized in that an effective amount of at least one compound of formula (I) as claimed in claim 1 or a herbicidal composition as claimed in claim 7 or 8 is applied to plants or the site of unwanted vegetation . Use of a compound of formula (I) according to claim 1 or a herbicidal composition according to claim 7 or 8 for controlling unwanted plants. The use according to claim 10, characterized in that the compound of formula (I) is used for controlling unwanted plants in crops of useful plants. The use according to claim 11 is characterized in that the useful plant is a gene-transformed useful plant.

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